Process for dyeing hair with substituted 2, 4-diaminophenols



3,184,387 PROCESS FOR DYEING HAIR WITH SUBSTITUTED 2,4-DIAMINOPHENOLSJohn Robert Seemuller, Maisons-Lafitte, Seine et Oise, France, assignorto LOreal, a corporation of France N Drawing. Filed Dec. 7, 1959, Ser.No. 857,989 Claims priority, application France, Nov. 25, 1955, 703,367,Patent 1,137,922; Oct. 18, 1956, 57,825 Claims. (Cl. 167--88) Thisapplication is a continuation-in-part of my copending application ofSerial No. 623,773, filed November 23, 1956, which application is nowabandoned.

This invention relates to the dyeing of animal fibres, and moreespecially the dyeing of live hair, by the use of polyaminophenolcompounds and derivatives thereof.

It has long been known to elfect the dyeing of hair with the aid ofso-called oxidation dyes, which are not true dyes but products which, onoxidation, give colored derivatives. The known oxidation dyes aregenerally aromatic polyamines and/or polyaminophenols.

Generally in using oxidation dyes a solution of such a dye is mixed, ashort time before use, with an oxidizing solution, for example dilutehydrogen peroxide, and the mixture is then applied to the hair to bedyed. Satisfactory results are obtained, but this method offers thedisadvantage that the treatment is of excessively long duration, thehydrogen peroxide tends to act deleteriously on the substance of thehair during the application, and it is necessary to store the workingsolutions in separate bottles.

It has now been found that polyaminophenols of the general formula:

wherein R and R designate a member of the group consisting of a hydrogenatom, a lower alkyl group or a lower hydroxyalkyl group; one or theother of the groups R and R must be other than hydrogen.

These compounds have remarkable properties as oxidation dyes for thedyeing of animal fibres and more especially of the human hair. The saidcompounds oxidize rapidly in the air so that the use of an auxiliaryoxidizing agent, such as hydrogen peroxide, is avoided, together withthe concomitant disadvantages referred to above.

According to the present invention therefore, a process for dyeing livehair comprises applying to the fibres a solution of a compound of theaforesaid general formula, allowing the oxygen of the ambient air to acton the hair impregnated with the compound for a time sufiicient to thedesired development of the shade, and thereafter rinsing the hair.

An aqueous solution of these compounds or of their derivatives isprepared, the pH of the solution is adjusted with the aid of an alkali,for example ammonium hydroxide, and the solution is applied to thefibres to be dyed, for example to the human hair. By simple exposure tothe ambient air, the fibre is dyed to a shade depending upon thederivative chosen. The process is very simple, avoids the use of anoxidizing agent such as dilute hydrogen peroxide, and permits dyeing atroom temperature.

The present invention further provides compositions for application toanimal fibres for dyeing the same, comprising an aqueous solution of acompound of the aforesaid general formula adjusted to a pH value of 5 to8.

United States Patent 0 Patented May 18, 1965 "ice EXAMPLE I2-methylamin0-4-aminophenol EXAMPLE II4-beta-hydr0xyethylamino-Z-aminophenol NIL-011 011 011 Potassium2-nitro-4-aminophenate is condensed with glycol chlorohydrin inalcoholic solution. There is thus obtained4-beta-hydr0xyethylamino-2-nitropheno1 melting at 114115 C.

Analysis:

Element Calculated Found C. 48. 5 48. 3 I 5. 05 4. 86 N 14.14 14. 21

This compound is then reduced to obtain the desired compound, which isisolated in the form of its sulphate, melting at C.

Dyeing.-By operating under conditions similar to those of the foregoingexample a beautiful violet shade is obtained on live hair.

EXAMPLE III 4-methylamino-2-amin0phenol NH-CH;

This compound is prepared in the following manner:N-methyl-paraminophenol is acetylated, then nitrated by the classicalmethod. Then it is deacetylated to obtain the4-methy1amino-Z-nitrophenol, which gives by reduction using the usualtechnique, the 4-methylamino-2-aminophenol which is isolated as thesulphate.

Dyeing.-This material is used in a manner analogous to that described inthe preceding examples. A 3% sulphate solution is applied to live humanhair having a pH adjusted to 8 by the addition of ammonium hydroxide.This allows the dyeing of white hair a deep blue shade.

In order to clearly show the particular possibilities of the use of thecompounds according to the invention, all

. 3 V the dyeing tests described in the foregoing examples were carriedout without any oxidizing agent other than atmospheric oxygen.

' What is claimed is:

1. A process for dyeing live human hair which com-.

prises: applying to the-hair an aqueous solution as' an oxidative dyestuff of a compound of'the formula NHRr wherein R and R are selectedfrom the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, and at '3. A process for dyeing live human hairrwhich comprises:applying thereto an aqueous solution as an oxi- V "'dative dyestutfcontaining Z-methylamino-4aminophenol,

least one of R and R are other than hydrogen, thereafter said hair isaerated to promote the substantial oxidation of this compound beforebeing rinsed. 1

2. A process for dyeing live human hair which com prises: applying tothe hair an aqueous solutionas an oxidative dye stuff adjusted to a pHof 5 to 8 of a sulphate of a compound of the formula I THRI wherein Rand R are selected fromthe group consisting of hydrogen, lower alkyl andlower hydroxy alkyl, and at least one of R and R are other thanhydrogen, thereafter said hair is aerated to promote the substantial oxidation of this compound before being rinsed.

7 May 1954, pp. 345-348.

thereafter said hair is aerated to promote the substantial oxidation ofthis compound before being rinsed.

prises: applying thereto an aqueous solution, as an oxidative dye stuff,containing 4-methylarnino-2eaminophenol,

' thereafter said hairis aerated to promote the substantial oxidation ofthis compound before beingrinsed.

References Cited by the Examiner UNITED STATES PATENTS 7 1,853,455 74/32 Reddelien et a1. 260573 FOREIGN PATENTS 7/11 France. 7

Addition to 413,877.

OTHER REFERENCES Chemical Abstracts, vol. 12: 1781 1918 Heilingotter:Am. Perfumer and Essential Oil Review,

Kaas I: Am. Perfumer and Aromatics, 68: 1, July 1956, 25-28.

Wood: Chemical Abstracts, vol. 46 (1952), col. 10117i.

JULIAN s. LEVITT, Primary Examiner.

.S. ROSEN, FRANK CACCIAPAGLIA, JR., LEWIS GOTTS, Examiners. v

1. A PROCESS FOR DYEING LIVE HUMAN HAIR WHICH COMPRISES: APPLYING TO THEHAIR AN AQUEOUS SOLUTION AS AN OXIDATIVE DYE STUFF OF A COMPOUND OF THEFORMULA